High-Frequency Mass Transfer Enabling Over-Limiting Currents in Porous Electrodes

Abstract

Classical film theory predicts a finite diffusion-limited current at porous electrodes. However, over-limiting currents (OLCs), which exceed this limit, are often observed and have been attributed to surface charge, confinement, or electrokinetic effects. Here, we use a frequency-domain framework to identify a different mechanism governed by the time scale of concentration variation. For perfectly reactive interfaces, the spectral Sherwood number, a frequency-dependent dimensionless measure of interfacial mass transfer relative to molecular diffusion, grows as $\Shnd\simω^{1/2}$ at high frequency, while its phase approaches $π/4$. This response corresponds to the semi-infinite Warburg limit of the electrochemical impedance. A scaling analysis shows that the exponent and prefactor are determined by diffusion within a thin layer adjacent to the interface and are therefore independent of the global pore geometry. Numerical results for parallel plates, circular tubes, and twelve porous microstructures confirm this scaling. Geometry, flow strength, and flow direction affect the low-frequency response and crossover frequency, but not the asymptotic scaling in the high-frequency limit. This temporal route to OLCs requires neither surface charge nor confinement and could inform the design of systems for pulsed electrodeposition, mineral recovery and renewable-energy storage.